Certain water-soluble high molal oxyalkylated esters: and method of making same



Patented NovlZl, 1944 CERTAIN WATER-SOLUBLE HIGH Mom OXYALKYLATED ESTERS: AND ME'rHon UNITED;

MelvirifDeGroote, University City, andBernhard Keiser, Webster Groves, M assignors to Petrolit'e Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Original application July @1941, Serial N 0. 401,378. Divided and this application March 9, 1943, Serial No. 478,589

' 12 Claims. ((21,26054045) This invention relates to a newchemical product, our present application being a division of our pending application for patent Serial No. 401,378, filed July 7, 1941, for Process for breakglycol, octaet'hylene" glycol, nonaethylene glycol,

I formula:

decaethylene glycol, to and including heptadecaethylene glycol. For convenience these polyethylene glycols may ing petroleum emulsions, which subsequently oHwilmoomH mawredas Patent Q- 2,324,490: dated July in which m varies from 7through 17. I 2 9 y I y Instead ofpolyethylene glycols, one may use Wl l Thus, for convenience, in e roa es aspec e i lw ly 3 y fi t polyalkyleneglycols employed may be indicated resoiu 1011 0 cm e o em sions; the following formula;

Another object of our invention is toprovide y H O);

a practicable methodformanuiacturing said new OH t m l l a p f d PO in which mhas its previous significance, and 11 h h e i th p ry l' of P represents a numeralvaryingfroin 2 to 4.

e t o 15 0 D QV d nfiw mpound or Thus, the bulk of th materials hereincontemcomposition of matter that isj an eificient deplated, particularly for use as demulsifiers, may mulsifier forhcrude1 o l emulstiions o h w r; be indicated within certain variations, as hereinin-oil type, t e sai compoun or composi ion o fter tated, by the neutral ester derivedby matter may be employed i other arts, as 11G 35 esterification of one mole of a glycol of the kind me iirter'mdmafed 1 r d ft above described, with two moles of a fractiornal new 0 emlca compoun composl ester of the kind previously described? he matter here n s e is eXeInplified b t formation of the compound may be indicated by acidi? t lg f fg g y, i 615m; l l kg the following reaction, although obviously, it is p 6 8 e5 9 OP 1? 0 a P Ya Y immaterial what particular procedure is; employed it;i351???iifiififiii ifif dliifi fifi fi i the particular mammal l l l produc: a l l hydroxylated material of the kind herein denl y l i scribed, and a polybasic carboxy acid having not 36 -9- over six carbonatoms. l If a hydroxylated material, indicated for t TLOOC.DJCOO(C2H4O)m-1C2H4.OOCZD.COO.T sake of convenience by the formu1a.T.OH, in q which 'I is an alcohol residue, is reacted with a m m t 'i pr m polybal'slc acllds polybasic -carboxy acid, which, similarly, may f' hmlted t e y havlng not q conveniently be indicated as being ofthedibasic n l t l f Fl q typeyby theformula :HOOQDCOOHLm which malon c succinic, glutaric, andadlplc. Smnlarly,

.D isa dicarboxy acid residue ,thenthe fractional one a 9 acfqs u h as l' t ester obtained by reaction between equimolar l i i m fii mcmdmg quantitiesmay belindicated by the following i. i of formula: l l 1 t 0 the particular tribasic orldibas c ac d employed HOOCD 0 is usually concerned largely with convenience i i h y of manufactureofthe' finished-ester, and also of The polyethylene. glycolmay becharacterizedfby the price of the reactants. Generally speaking} materials of the] kind such as hptaethylene the higher the ter nperature e mployed, the easier it is to obtain large yields of the esterified prod be indicated'by the following l uct. Although oxalic acid is comparatively cheap, it decomposes somewhat readily at slightly above the boiling point of water. For this reason, it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is particularly adaptable; and. also, everything else considered, thecost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or th anhydride has many of the attractive qualities of maleic anhydride; and this is'also true of adipic acid. For purposes of brevity, the bulk of the compounds hereinafter illustrated will refer to the use of maleic an-, hydride, although it is understood that any other suitable polybasic acid may be employed. Fur- 8-12 oxyalkylene groups, particularly 8-12 oxyethylene groups. Th preference to use the oxyethylated compounds is dueglargely, to the fact pears to be largely monomeric. For convenience,

such intermediate product may then be considered as a dibasic or polybasic acid. One mole of the intermediate so obtained is then reacted with two moles of the alcoholic material of th kind subsequently described.

It is to be noted, however, that if one prepares a fractional acidic ester, then if two moles of K'the fractional acidic ester are reacted with one mole of the polyethylene glycol, there is no possibility for the formation of polymeric types of esterification products under ordinary conditions.

The alcoholic" compounds employed as reactants in one mode of manufacture of the present compounds are basic hydroxylated acylated poly- ,amino compounds free from ether linkages. Such compounds are described inter alia in U. S. Patent No; 2,243,329, dated May 27, 1941, to

' De Groote and Blair. For instance, this particuthat they are commercially available, and particularly so in two desirable forms. The most desirable form is the so-called nonaethylene glycol,

which, although consisting largely of nonaethylene glycol, may contain small amounts of hepta-v ethylene and octaethylene glycols, and possibly minor percentages of the higher homologs. Such glycols represent the upper range of distillable glycols; and they may be conveniently referred to as upper distillable ethylene glycols. There is no particularly good procedure for making a. sharper separation on a commercial scale; and it is understood that mixtures of one or more of the glycols may be employed, as well as a single glycol. As pointed out, it is particularly preferred to'employ nonaethylene glycol as commercially available, although it is understood that this glycols would cause some higher homologs to be formed; and, thus, even in this instance, there may be present some oxyethylene glycols within th higher range above indicated. One need not point out that these particular compounds consist of mixtures, and that in some instances, particularly desirable esters, are obtained by making mixtures of the liquid nonaethylene glycol with the soft, waxy, lower non-distillable polyethylene glycols. For the sake of convenience, reference in the examples will be to nonaethylene glycol; and calculations will be based on atheoretical molecular weight of 414. Actually, in manufacture, the molecular weight of the glycol employed, whether a higher'distillable polyethylene glycol or a lower non-distillable polyethylene glycol, or a mixture ofthe same, should be determined and reaction conducted on the basis of such determination, particularly in conjunction with the hydroxyl or acetyl value.

lar patent describes a basic type acylated polyamine of the following formula:

2 I 2 \NC ,.H2n(CnH2,.NZ),N

radical derived from a, lower'molecular weight carboxy acid having 6 carbon atoms or less; and

D is a member of the class consisting of alkyl,

hydroxyalkyl, aminoalkyl, and acyloxyalkylene',

, in which instance the acyl group is a member of the class consisting of RC0 and R'CO'; and

. the acylated polyamine is further characterized by the fact that there must be present a member of the class consisting of (a) Acyloxyalkylene radical in which the acyl group is RC0; and

(b) Joint occurrence of .an amido radical in which the acyl group is RC0 and a hydroxyalkyl radical.

Needless to say, compounds of the kind therein described may be derived from polyamines having only two amino nitrogen atoms, as differentiated from polyamines having 3 amino nitrogen atoms or more. may represent zero, as well as the numeral 1 to 10. It is obvious that numerous examples of the compounds indicated by'the above formula are hydroxylated, due to the presence of one ormore hydroxylated radicals of the following types:

(a) There may be present a hydroxyethyl group or a hydroxypropyl group or the like;

(Z7) The acyl group of the higher molecular weight carboxy' acid may contain a hydroxyl group, as, for example, ricinoleic acid, hydroxystearic acid, etc.;

(0) The low molecular weight carboxy acid present may have a hydroxyl' group in the acyl Thus, in the above formula, as

. 2,363,048: radical; such. as. would be the case whenithe radical is derived fromlactic acid; and

(d) The amines above described may becon-j sidered as derivatives of dichloralkanes or alkylene, dichlorides. This is discussed clearly in the aforementioned De Groote and Blair patent. If

such amines, whichareiderivatives of propylene dichloride, as indicated by the following compoit is obvious that another-means is available for introducing an alcoholiform hydroxyl radical. Since this particularapplication or modification is extremely narrow in scope, and applies only to theinstances where thealkylene group is a propylene radical, it is understood that in the hereto appended claims it is intended that wherever a propylene group is included, the hydroxy propylene group is considered asthe functional equivalent, for the reasons stated. 1

Although in the compounds above described the radical RCO may bederived from a higher molecular weight carboxy acid, in the present instance the invention is concerned with the particular type, in which RC is derived from a more narrow class, to wit, etergent-forming monocarboxy acids. A I 1 It is well known that certain monocarboxy organic acids "containing eight carbon atoms ormore, and not more than 32 carbon atoms,

are characterized by the fact that they combine with alkalies to produce soap or soaplike materials. These detergent-forming acidsfinclude fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will beindicated by the formula R.CO0H. Certain derivatives of detergent-forming acids react with alkali to produce soap or soap-like materials, and are. the obvious equivalent of the unchanged or unmodified detergent-forming acids, for instance,

instead of fatty acids, one might employ the chlorinated fatty. acids. .Insteadof the resin acids, one mightemploy the hydrogenated resin acids Instead of ,naphthenic acids, one, might employ brominated naphthenic acids, etc. I

The fatty acids are of the typecommonl'y referred toas higher fatty acids; and of course, i this, is also true inregard to derivatives of the kind indicated, insofar that such derivativesare obtained from higher fatty acids. The petroleum acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oxidation of wax, paraf fin, etc. Such acids may have as many as 32 carbon atoms. For instance,

, see U. S. Patent No. 2,242,837, dated May 20, 1941, to Shields.

We have foundthat the new composition of matter herein contemplated, which is most valuable as a demulsifier, is preferably derived from unsaturated fatty acids having 18 carbon atoms. Such unsaturated fatty acids include the fatty acids,such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obtained from hydrolysis of cottonseedoil, soya bean oil, etc. Our preferreddemulsifier'is o'btained from unsaturated. fattyacidaand moreespecially, unsaturatedv fatty acids, which have, been, subjected to an oxidation or oxyalkylation step, such as oxyethylation. Of the various unsaturated'fatty acids, ourchoic'eis the hydroxyl ated type, to wit, ricinoleic acid. H N f For. purposes of? brevity, f.'the bulk of any subsequent description will .be concerned with fatty acids, and particularlyunsaturated] fatty acids, Further reference to other detergenttype monocarboxy acids is quite limitedsbutatten- .tion is directed to the fact that anjadequate description is found in the aforementioned De Groote and Blair patent. The following examples are substantially as they appear in said patent. One must not forget, however, that in addition to the amines described insaid patent as reactants, one can also use reagents such as ethylene diamine, bis(hydroxyethyl)ethylene diamine, tris(hydroxyethyl)ethylene diamine, etc. In view, of what is said in the aforementioned De Groote and Blair patent, itwill be obvious why the description of the amide is given as a primarily raw material.

Amide-Ema1hple .1

283 parts of stearic acid amide are heatedwith. 438 parts of triethylene tetramine for 10 hours to about 130 C. until a test portion issoluble in diluted hydrochloric acid; at the endof the reaction the pressure is preferably lowered to about 1'5 mm. Hg. Thereby 380 partsof a productprobably correspondingto the formula ,cl naconmoznmmion-1mm (monostearyl triethylene tetramine) are ob- .231 parts of oleic acid amide yield with 584 parts of triethylene tetraminawhenheated for 10 hours to about 130C.,;400 parts of a product which is soluble in diluted hydrochloric acid, and probably corresponds to the monooleyl triethylene tetramine. AmideExampZe 3 283..parts of stearic acid amide are heated in the same way as described in Examples 1 and 2 l with 400 parts of a mixture of polyalkylene polyamines obtainable by heating ethylene dichloride with ammonia under pressure and removing any ethylene diamine formed during the latter reaction. After distilling the excess of bases under reduced pressure, 430 partsof a paste are obtained which is soluble in diluted acids.

Amide-Example 4 300 parts of ricinoleic acid amide mad with 6d 400 parts of a mixture of bases according to Example 3, when heatedfor about ,8 hours to 150- 160 C.,450 parts of a mixture of a cylated bases which is easily soluble in diluted acetic or hydrochloric acid.

' Amide--Example5 From 300 parts of ricinoleic acid amideand 400 parts of a mixture of polyalkylene polyamines according to Examples 3 and4, by heating for severalhours to C., simultaneously passing a current of dry air free from C02, and finally removing the excess of bases partly by distilling underreduced pressure andapartly by washing with Water, there are obtained430 parts of a mixture ofpolyalkylene polyamines whichis acylated by the radical of ricinoleic acid.

Amide-Example 6 100 parts by weight of olive oil and 100 parts by weight of diethylenetriamine are heated to about 180-200 C. until a test portion of the reaction mixture is soluble in dilute hydrochloric acid. After' distilling off the excess of diethylenetriamine, advantageously under reduced pressure, there remains a strongly viscous mass, the hydrochloric acid solution of which has great foam-forming properties. a

A similar product is obtainable by heating free oleic acid with a large excess of diethylenetriamine under the same conditions.

Amide Example' 7 310 parts by weight of the ethylester of oleic' acid are heated with 286 parts by weight of triethylene tetramine at about 160 C. for 12 hours when a homogeneous solution is formed; the al- 'cohol formed and the excess of triethylenetetramine are distilled off. The residual reaction product forms a brown oil, which is diflicultly soluble in water and readily soluble in alcohol, benzene and dilute hydrochloric acid.

A quite similar product is obtainable by heating tree oleic acid with an excess of triethylene tetramine to about ISO-200 C. and distilling ofi the excess of triethylenetetramine under reduced pressure.

200 parts by weight of olive oil are heated at 180-200 C. with 300 parts byweight of a mixture of bases, which is obtained by the action of ammonia on ethylene chloride at 80-120 C. under pressure of 10 atm. and after distilling off the ethylene diamine, said mixture of bases boiling at about 15 mm. mercury between 90 and 300 C. When a test portion ofthe reaction product is smoothly soluble in dilute hydrochloric acid, the water formed. and the excess bases are distilled off under reduced pressure and a yellowish brown oil is obtained, a solution of which in dilute hydrochloric acid can be used as a washing or wetting agent.

Amide-E:tample 9 350 grams of monostearin and 300 grams of triethylenetetramine are heated together at l80-200 C. for 3 to 4 hours and then the displaced glycerine and the excess triethylene-tetramine were washed out with water and the resulting product dried.

Amide Ea:ample 10 In the prior examples tetraethylenepentamine is substituted for the amines employed in the prior examples by using a suitable molecular equivalent, but without increasing the amount of fatty acid compound employed.

Amide-Ea:ample 11 Purified n aphthenic acids derived from Gulf Coast crudes are employed in various examples preceding.

Amide-Example 12 Carboxy acids derived from oxides of Pennsylvania crude oil and having approximately 10-14 carbon atoms per mole of fatt acid, are substituted in the previous examples.

Basic type oxyallcylation compound of amido derivative of polyamine- --Intermediate Example 1 Materials of the kind described in Amide, Examples Nos. 1-12, preceding, are treated with one mole of ethylene oxide in the manner previously described, so as to introduce one hydroxyethyli radical. Such reaction may be illustrated in the following manner? It is to be noted that in the above reaction, the ethylene oxide radical adds at the basic amino nitrogen atom, although obviously, it might add at the non-basic amido nitrogen atom.

Basic type oxyalkylation compound of amido derivative of poZyamine-Intermediate Example 2 The same procedure is followed as in the preceding example, except that more than one hydroxyalkyl group, or rather, hydroxyethyl group, is introduced, the preference being to introduce two or three hydroxyethyl groups.

Basic type oa'yalkylation compound or amido derivative of polyamine1ntermediate Example 3 Propylene oxide is substituted for ethylene oxide in Examples 1 and 2, preceding.

Basic type oxyallcylation compound of amido derivative of poZyamine-Intermediate Example 4 Glycid is substituted for ethylene oxide in Examples 1 and 2, preceding.

The ethylene oxide may, of course, combine with the hydrogen atom attached to the central amino nitrogen atom. I

- Oryalkylation derivatives of pol'yamine- Example 2 Triethylene tetramine is substituted for diethylene triamine in Example 1.

Oacyalkylation derivatives of polyamine- Example 3 Tetraethylene pentamine is substituted for diethylene triamine in Example 1.

Org/alleviation derivatives of polyamine- Example 4 Pentaethylene hexamine is substituted for diethylene triamine in Example 1.

Basic type acylation derivative of oxyalkylated polyamineIntermediate Example 5 A material of the kind described in Oxyalkylation derivatives of polyamine, Example 1, is acylated in the same manner in which amides are obtained in Amide, Examples'1-12, previously de- 2,303,048 scribed Such acylation reaction may. be illustrated thusz i in which R2000 represents a higher fatty acid or the like. s

Basic type acylat ion derivative of omyalkylated V s polyamine lntermediate Example A material of thekind described in Oxyalkylation derivatives of polyamine, Example 2, is acylated in the same manner in whicha'mides are obtained in Amide, Examples 1-12, previously described. y i i Basic type acylation derivative oxyalkylated poZyamine-Intermedi te Example 7 A material of the kind described in Oxyalkylation derivativesof'polyamine, Example 3, is acylsimply as if involvingflthe acid instead or the anhydride. thus:

HO oceanic o ogtifiipjcuucnsoemn W cns'giiir'gioo comic 0 on Glycol ester intermediate producprmm ze 2 A mixture of lower non-distillable polyethylene glycols, representing approximately decato tetradecaethylenetglycol, is substituted for nonaethlyene glycol in the-preceding exa/mple.

Glycol ester intermediate roducprmm ze 3 a 1 A. 50-50 mixture of ,nonaethylene glycol and lower nondistillable polyethylene glycolsgof the kind-described in the previous example is substituted for nonaethylene glycol in Example 1.

Glycol ester intermediate produet-Erample '4 Adipic acid is substituted for maleic anhydride in Examples 1- 3, preceding. M

ated in the same manner in which amides are obtained in Amide, described.

. Basic type re-acylated oxyalkylation compound of amido deriuatiue of p0ly mine-Intermediate Example 9 Materials of the kind exemplifiedby Intermediates 1-4, preceding, which have beenidesignated for convenience as .Basic type oxyalkylation compound of amido derivative of polyamine, i.

e., prepared byconverting the polyamine into an amide and then subjecting the same to oxyalkylation, may, of course, be re-acylated or acylated further, so as to introduce, acylgroupsof the kind described. Under such circumstances, one

invariably obtains the mixed type, i; e., the esteramide type, provided thattherehas been total oxyalkylation. "Excellent.intermediates are obtained. by such process, i.e., the re-etcylation, or second acylation, of materials of the kfind exem plified by Intermediates 1-4, inclusive, and par.

ticularlywhen such re-acylation takes place by Examples 151-2, previously means of detergent-forming acids, whichpin the preferred form, are illustrated by fatty acids, and more particularly, by the hydroxylated fatty acid: type. The preferredflmember of this type, in the present instance, as in other instances, is rich:-

oleic acid. Having obtanedbasic hydroxylated polyamine compounds of the kindpreviously described, the

next step is to obtain fractional esters derived from nonaethylene glycol of the kind described in the earlier part of the present disclosure. Such materialsmay be illustrated by the following examples:

Glycol ester z'nteiu'rueriz'ltte product-Erra1hpla1 One pound mole. of nonaethylene glycol is treated withtwoipound moles of maleic anhydride, so as to formjnonaethylene glycol dihydro-f gen dimaleate. The reaction may be shown more lycol ester interm edz'ate product-Trample .5 Oxalicacid is substituted formaleic anhydride in Examples 13,preceding. s Glycol ester i ntcrmedia te productE:mmjJZe 6 1 Citric acid is substituted for maleic anhydride inExamples 1-3 preceding."

Glycol. ester intermediate product-Example.

jSuccirriclanhydride ishsubst ituted for maleie anhydride'in Examples .1 3, preceding.

The method of producing such fractional esters is well known. The general procedure is to employ a temperature above the boiling point of waterrand below the pyrolytic point of the'reactants. The products are mixed and stirred cone stantly during the heating and esterification step;

If desired, an inertga's, such as dried nitrogen,

or dried carbon dioxide, may be "passed through the mixture. Sometimes it is desirable to add an esterification catalyst, such assulfuric acid, benzene sulfonic acid, or. the like This is the same general procedu e as employed in the mjanufac ture of ethylene glycoldihydrogen diphthalate.

See U. S. Patent No.2,075,1 07, dated March 30, s

1937, to Frasier. i i i r i Sometimes esterification is conducted most readily in the presence 10f an. inert solvent that i carries away the Water of esterificationyvhich may be formed, although, as is readily appreciated, such water chesterification is absent when: the reaction involves an acid anhydride,

such as maleic anhydride, and a glycoln However,

if water is formed, for instance, whencitric acid is employed, thenasolvent such asxylene may be present and employed tocarry off thewater formed. The mixture of xylene vapors and water vapors can be condensed so that the water is separated. The, xylene is then returned to the reaction Vessel for. further circulation. This is a conventional and.well-knownfprocedure, and.

requires no ,further elaboration.

Composition of flatten-Example l Two pound moles of a material. exemplified Basic type oxyalkylation compound of armdo derivative of polyaminaxIntermediate Example 1, arereactedwith onefpound moleof a glycol ester intermediateproduct of thekind described under Glycolester intermediate products, Examples 1,

2 and 3, preceding. Suchtreaction is continued until all the carboxylzacidityhasd sappeared.

The time of reaction may vary from a few hours to as many as 20 hours.

Composition of matter-Example 2 Basic type oxyalkylation compound of amido derivative of polyamine, Intermediate Example 2, is substituted for Basic type oxyalkylation compound of amido derivative of polyamine, Intermediate Example 1, in the example preceding.

Composition of matte1Ea.'ampZe 3 say any particular method may be used to produce the desired compounds of the kind indicated. In some instances, it may be desirable to conduct the esterification reaction in the presence of a non-volatile inert solvent which simply acts as a diluent or viscosity reducer.

In the preceding examples, attention has been directed primarily to the monomeric form, or at least, to the form in which the bifunctional alcohol, i. e., a glycol, and the polyfunctional acid, usually a bifunctional compound, react to give a chain type compound, in which the adjacent acid and glycol nucleus occur as a structural unit. For instance, in the monomeric form this may be indicated in the following manner:

acid....glycol.... I

If, however, 'one prepared an intermediate product employing the ratio of three moles of maleic anhydride and two moles of nonaethylene glycol, the tendency would be to produce a product which might be indicated in the f ollowing manner:

acid glycol acid glycol acid Similarly, three moles 'of the glycol and. four moles of the acid might tend to give a combination which may be indicated thus:

acid glycol acid glycol acid glycol acid Another way of stating the matter is that the composition may be indicated in the following manner:

acid

in which the characters have their previous significance and a: is a relatively small whole number less than 10, and probably less than 5; and in the monomeric form :L', of course, is l. The limitations on the size of :r are probably influenced largely by the fact that reaction leading to further growth is dependent upon random contact.

Some of the products are self-emulsifiable oils, or self-emulsifiable compounds; whereas, others give cloudy solutions or sols; and the most desirable type is characterized by giving a clear solution in water, and usually in the presence of soluble calcium or magnesium salts, and frequently, in the presence of significant amounts of either acids or alkalies.

Water solubility can be enhanced in a number of ways which have been suggested by previous manufacturing directions, for instance:

(a) By usinga more highly polymerized ethylene glycol (b) By using a polymeric form instead of a an acid monomeric form in regard to the unit which forms the chain between the two alcoholic nuclei;

(o) By using a polybasic carboxy acid of lower molecular weight, for instance, maleic acid, instead of adipic acid; and

(d) By using. an amino body having fewer high molal acyl groups, or more amino nitrogen atoms, or any other obvious variant.

Indeed, in many instances the acylated polyamino, compound is water-soluble prior to reaction with the glycol ester. It is to be noted that in this instance one is not limited to hydroxylated materials which are Water-insoluble prior to reaction with a glycol ester; but they may, in fact, be perfectly water-soluble.

Actually, a reaction involving an alcohol and (esteriflcation) may permit small amounts of either one or both of the reactants, depending upon the predetermined proportion,

to remain in an unreacted state. In the actual.

preparation of compositions of the kind herein contemplated, any residual acidity can be removed by any suitable base, for instance, ammonia, triethanolamine, or the like, especially in dilute solution. Naturally, precaution should betaken, so that neutralization takes place without saponification or decomposition of the ester. In some cases there is no objection to the presence of the acidic group. Indeed, if a tribasic acid be employed. in such a manner as to leave one free carboXyl-group, then it is usually desirable to neutralize such group by means of a suitable basic material.

In the hereto appended claims, reference to a neutral product refers to one in which free carboxylic radicals are absent.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifiers for cosmetics, spray oils, waterrepellant textile finish, etc. These uses are by no means exhaustive.

However, the most important phase of the present invention, as far as industrial application goes, is concerned withthe use of the materials previously described as demulsifiers for water-in-oil emulsions, and more specifically, emulsions of water or'brine in crude petroleum.

A somewhat analogous use of our demulsifying agent is the removal of a residual mud sheath which remains after drilling a well by the rotary ,method. Sometimes the drilling mud contains added calcium carbonate or the like to render the mud susceptible to reaction with hydrochlo-' ric acid or the like, and thus expedite its'removal.

Chemical compounds of the kind herein described are also of value as surface tension de pressants in the acidization of calcareous oilbearing strata by means of strong mineral acid, such as hydrochloric acid. Similarly, some members are efiective as surface tension depressants or Wetting agents in oil-bearing strata.

catedby the following formula:

the flooding of exhausted As to using compounds of the kindherein de- 3 scribed as :fiooding agents for-recoveringoil from subterranean strata, reference is made to the procedure described in detail in U, S. Patent No.

2,226,119, dated December 24, 1940, to De Groote and Keiser. As to usingcompounds of the kind hereindescribed as demulsifiers, or particular as surface; tension depressants, :in combination with mineral acid or, acidization of oils-bearing strata, reference, is made to U. S. Patent No. 2,233,383, dated February 25, 1941, to DefGroote and Keiser, ff

It will be apparent to those skilled in the art that residual carboxyl acidity ,can be eliminated by esterification with a low molal alcohol, for instance, ethyl, methyl, ,orpropyl alcohol, by conventional procedure, soas to givea substantially neutral product. Theintroduction of such low molal hydrophobegroups does, not seriously affeet the solubility, and in some instances, gives increased, resistance, to soluble calcium and magnesium salts, for such property, isof particular value. Usually, however, neutralization with a dilute solution of ammonia or the like, is just as practicable and less expensive, i In, the heretotappendediclaims, it ,is

that the monomeric forms contemplate also the polymeric forms, insofar, that the polymeric forms are nothing more or less than a repeti- :tion of the monomeric forms several times over,

with the lossof oneormore "moles of water.

What has just been said can berecapitulated and presented in more formal agreement/with customary nomenclature in, the following man ner: Asstatedpreviously in the broadest aspect,

the polyalkylene ,glycols employed may be indi- OH(C1ZH21LO)7TLH in which m has its previous significance, and n represents a numeral varying from 2 to 4. In

simple-form, this structure can be indicated in thefollowing manner: i e i HO--R--OH in which the divalentradical ,-RO- is the divalent radical --(C'nI-I21LO) mas previously defined. i i

The dibasic acid previously referred to, inits simplest form as HOOCDCOOH, is more completely portrayed by the following formula 5 in which R1 is the'polybasic carboxy acid residue, except in the unique case of oxalic acid,

and 1t is the numeral or 1, depending upon whether or not the polybasic acid isdibasic or tribasic. i

If the polybasic acidjust described is indicated by R, and if the glycol just described is indicated byRf', thenthe acidic or fractional ester previously described in the specification may be indicatedby the following formula:

12:1 to p+1,:p', with the obvious proviso that such ester must contain at least two free carboxyl radicals. M r i i v i Previous reference has been made to the hydroxylated acylated polyamino compound free from ether linkages and of the followingcomaminoalkyl, and acyloxyalkylene, in which inintended in which m varicsfrom 11 to 1o, R7 is the radigroup is R4CO; and

stance the, acyl group is a member of the class consisting of R4C0; and;RCO;and the acylated polyamine is further characterized, by the fact that theremust-be present a member of the class consisting of i i a (a) Acyloxyalkylene radical, in which the acyl (17) Joint occurrence of an amide radical, in which the acyl group is R400 and a hydroxyalkyl radical.

It is more convenient to cons iderthe previous e ,5 compound as an alcohol of the formula moms cal obtained by the dehydroxylation of the previously described basic hydroxylated acylated polyamino compound. It is to benoted that one or more of the hydroxyls may be part of an i acyl radical, such as a ricinoleyl radical, or part of an alkylol radical, such as an ethanol radical. In view of the fact that the amino com? pound may contain at least as many as five amino nitrogen atoms, and in view of the fact that the hydrogen atoms attached to all such amino nitrogen atoms maybe converted into alkanol radicals or hydrox yalkanol radicals by the action of ethylene oxide, or its equivalent,

or by the action of glycide, or its equivalenigand -since additionally certain acyl radicals, such as in which ppand p" represent numerals varying from 1 to 10, and p'flrepresents a numeral vary- ,ing from 1 to 20, and R and Rl'have their prior significance, andthe ratio of p to p'f varies from the ricinoleyl radical. may contain alcoholthydroxyl radicals, it is obvious that, considered as an alcoholic compound; the previously described poll/amino mpound'may have anywhere from 1 i 10 d xyl radicals. i it The composition of matter herein contem plated is best represented as an ester obtained by-the esterification reactioninvolving the acidic fractional ester above described and the hydroxylated acylated aminoalcohol previously depicted'in detail. The final composition may be obtained in any suitable manner, and would properly represent the final product, regardless of the succession of intermediate steps. So portrayed, the structural formula is asfollows: i

in which n represents a numeral varying from 1 to 10, iii represents a numeral varying from 1 to 4, and n"" represents a numeral varying from 1 to 10.

It has been previously pointed out in the specification that any residual carboxylic radicals, and especially one obtained from tribasic acids, could be neutralized with a variety of suitable basic materials. In other Words, a residual carboxylic hydrogen atom may be replaced by a metallic atom, ,an ammonium radical, or substituted ammonium radical, as previously indicated.

Under such circumstances, any residual carboxylic radical, instead of appearing thus: COOI-I, may, in essence, be the radical COORs represents a cation including the acidic hydrogen atom. This can be best disposed of by rewriting the formula for the polybasic carboxy acid, thus:

coon

R1O0OH in which all of the characters have their prior significance.

Having thus described our invention, what We claim as new and desire to secure by Letters Patent is:

l. A water-soluble esterjof the formula:

in which n" represents a numeral varying from 1 to 10, and nf represents a numeral varying from 1 to 4, and 12"" represents a numeral varyingfrom 1 to 10, and in which 10 and 1) represent numerals varying from 1 to 10, and the ratio of p to p varies from 2:1 to p+ 1:p', and p" represents a numeral varying from 1 to 20, and R is a in which R1 is the polycarboxy acid residue, and R8 is a cation, and n is the numeral or 1;

R7(OH)m"" is 'a hydroxylated acylated aminoalcohol in which m"" represents a numeral from 1 to 3, and R7 is the dehydroxylated residue of the hydroxylated acylated polyamino compound,

in which carbon atom chains are uninterrupted by oxygen atoms, and of the following composition:

in which m represents a small Whole number varying from 2 to a: is a small whole number varying from 0 to 10; R3 is a member of the class consisting of H, RiCO,v RsCO, and Rs, in which R400 represents an acyl radical derived from a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms, RsCO is an acyl radical derivedfrom a lower molecular weight carboxy acid having 6 carbon atoms or less; and R6 is a member of the class consisting of alkyl, hydroxyalkyl, aminoalkyl, and acyloxyalkylene, in which instance the acyl group is a member of the class consisting of R400 and R500; and the acylated polyamine is further characterized by the fact that there must be present a member of the class consisting of (a) 'Acyloxyalkylene radical, in which the acyl group is R4CO; and

(1)) Joint occurrences of an amido radical, in

which the acyl group is RiCO and a hydroxyalkyl radical.

2. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0.

3. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, resents the numeral 2.

4. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, and'm represents a numeral'varying from 7 to 11.

5. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, and RACO is an18 carbon atom fatty acid residue.

6. A water-soluble ester, as defined in claim -1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 tell, R400 is an 18 carbon atom fatty acid residue, and the ratio of p to p is 2 to 1.

7. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, R400 is an 18 carbon atom fatty acid residue, the ratio of p to p is 2 to 1, and with added neutralization of all residualacidity.

8. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from '7 to 11, RACO is a ricinoleic acid residue, the ratio of p to p is 2 to 1, and with added neutralization of all residual acidity.

9. A water-soluble ester, as defined in claim 1, wherein all occurences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, R400 is a ricinoleic acid residue, the ratio of p to p is 2 to 1, with added neutralization of all residual acidity, and R1 is an adipic acid residue.

10. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, R400 is a ricinoleic acid residue. the ratio of p to p is 2 to 1, with added neutralization of all residual acidity, and R1 is a succinic acid residue.

11. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, R400 is a ricinoleic acid residue, the ratio of p to p is 2 to 1, with added neutralization of all residual acidity, andR1 is a maleic acid residue.

12. In the manufacture of the esterification product of the kind described in claim 1, the steps of: (A) esterifying a polyalkylene glycol having at least 7 and not more than 17 ether linkages and the alkylene radical thereof containing at least one and not more than 6 carbon atoms, with a polybasic carboxy acid having not more than 6 carbon atoms, in a predetermined ratio of more than 1 and not more than 2 moles of the polybasic acid for each mole of the glycol, to produce a water-soluble product; (B) f esterifying one molal proportion of said alkylene glycol dihydrogen acid ester with 2 moles of a basic hydroxylated acylated polyamino compound and n repfreefrom ether linkages, of the following formula: ,n i z z nahmonmnmnn z n i z in which n represents a small whole number varying from 2 to 10; a: is a small wholenumber varying from 0 to 10'; Z is a member of the class consisting of H, RCO, RCO, and D, in which RCO represents an acyl radical derived from a detergent-forming monocarboxy acid; RfCO is an acyl radical derived from a lower molecular n less; andD is a member of the class consisting of alkyl, hydroxy alkyl, aminoalkyl, and wisdomweight carboxy acid having 6 carbon atoms or alkylene, in which instance the acyl group is a member of the class consistingof RC0 and R'CO;

and the acylated polyamine is further characterized bythe fact that there must be present a member of the class consisting of: (a) acyloxyalkylene radical in which the acyl group is RC0;

and (b) joint occurrence of an amido radical in which the acyl group is RC0 and ahydroxyalkyl radical.

1 MELVIN DE GRQO'IE. BERNI-IARD KEISER. 

